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Dimethylzinc-mediated additions of alkenylzirconocenes to aldimines. New methodologies for allylic amine and C-cyclopropylalkylamine syntheses

Wipf, P and Kendall, C and Stephenson, CRJ (2003) Dimethylzinc-mediated additions of alkenylzirconocenes to aldimines. New methodologies for allylic amine and C-cyclopropylalkylamine syntheses. Journal of the American Chemical Society, 125 (3). 761 - 768. ISSN 0002-7863

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Abstract

Hydrozirconation of alkynes with zirconocene hydrochloride followed by in situ transmetalation to dimethylzinc provides access to reactive alkenyl organometallic reagents from readily available precursors. Upon addition of imines, 1,2-attack leads to synthetically useful allylic amine building blocks. In the presence of CH 2 I 2 or CH 2 Cl 2 , the N-metalated allylic amide intermediate is cyclopropanated and C-cyclopropylalkylamines are formed in high yield and excellent diastereoselectivities favoring the anti products. The use of enynes as starting materials for this domino reaction provides conjugated biscyclopropanes and thus allows the stereoselective formation of five new carbon-carbon bonds. A transition state that explains the need for both zirconocene complex and alkyl zinc in the cyclopropanation reaction is proposed.


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Details

Item Type: Article
Status: Published
Creators/Authors:
CreatorsEmailPitt UsernameORCID
Wipf, Ppwipf@pitt.eduPWIPF
Kendall, C
Stephenson, CRJ
Date: 22 January 2003
Date Type: Publication
Journal or Publication Title: Journal of the American Chemical Society
Volume: 125
Number: 3
Page Range: 761 - 768
DOI or Unique Handle: 10.1021/ja028092a
Schools and Programs: Dietrich School of Arts and Sciences > Chemistry
Refereed: Yes
ISSN: 0002-7863
PubMed ID: 12526676
Date Deposited: 30 Jan 2014 20:55
Last Modified: 27 Apr 2019 14:55
URI: http://d-scholarship.pitt.edu/id/eprint/20440

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